Universidad EAFIT

Escuela de Ingeniera

Termodinmica
Propiedades de una Sustancia Pura
I.M. Luis Santiago Pars Londoo
2011

El Postulado de estado para una

sustancia pura, simple compresible
El estado de una
Sustancia pura (no mezclada ni contaminada)
simple compresible (solo un tipo de trabajo: el de
la deformacin de los lmites del sistema, es decir
en ausencia de efectos elctricos, magnticos, de
tensin superficial, elsticos, etc.),
y en equilibrio termodinmico,
est completamente determinado o especificado
por dos propiedades intensivas independientes.

Preguntas claves
Para el estado de una sustancia pura (sistema),
cuales son las dos propiedades intensivas
independientes?
R/: Depende si la sustancia est en una sola fase o
si coexisten varias fases.
Como se determinan el resto de propiedades
conociendo dos propiedades intensivas
independientes?
R/ Mediante las ecuaciones de estado, expresadas
en la forma de tablas, cartas o expresiones
matemtica, o en bases de datos especializadas.

Experimento:
Calentamiento de agua a Presin constante
P = 1atm

compressed
liquid
subcooled
liquid.

saturated
liquid.

saturated
liquidvapor
mixture.

saturated
vapor

superheated
vapor

Representacin grfica del Experimento:

Calentamiento de agua a Presin P constante
( De Lquido a vapor)
Datos y resultados del
Experimento:

P = 101.3 kPa
Tsat =100 C
vf = 0.001 m3/kg
vg = 1.67 m3/kg
vf

vg

Repeticin del calentamiento del agua a

diferentes Presiones.
(Proceso de cambio de fase)

Diagrama T-v de una sustancia Pura.

Identificacin de regiones

Diagrama P-v de una sustancia pura.

Identificacin de regiones

The 3D P-v-T surfaces present a great deal of information at once, but in a

thermodynamic analysis it is more convenient to work with 2-dimensional
diagrams, such as the P-v and T-v diagrams.

P-v-T surface of a substance that

contracts on freezing. (CO2)

P-v-T surface of a substance that

expands on freezing (like water).

Diagrama de fases P-T

A bajas
presiones (por
debajo del punto
triple), el solido
(hielo) se
evapora sin
fundirse primero
(sublimacin).

For water,
Ttp = 0.01C
Ptp = 0.6117 kPa

At triple-point
pressure and
temperature, a
substance
exists in three
phases in
equilibrium.

Resumen: diagramas P-v, T,v , P,T

Extending the
Diagrams to Include
the Solid Phase

P-v diagram of a substance that

contracts on freezing.

For water,
Ttp = 0.01C
Ptp = 0.6117 kPa
At triple-point pressure and
temperature, a substance
exists in three phases in
equilibrium.

P-v diagram of a substance that expands

on freezing (such as water).

Liquido saturado.
Vapor saturado.
Durante los procesos de
vaporizacin, evaporacin o ebullicin, o de
condensacin o licuefaccin,

las fases lquida y gaseosa coexisten en equilibrio

termodinmico.
En esta condiciones, el lquido se llama lquido
saturado y el vapor se llama vapor saturado.

Temperatura y Presin de Saturacin

The temperature at which water starts boiling depends on the pressure; therefore, if the
pressure is fixed, so is the boiling temperature.
Water boils at 100C at 1 atm pressure.
Saturation temperature Tsat: The temperature at which a pure substance changes
phase at a given pressure.
Saturation pressure Psat: The pressure at which a pure substance changes phase at a
given temperature.

The liquid
vapor
saturation
curve of a pure
substance
(numerical
values are for
water).

14

Temperatura de saturacin
Presin de saturacin.
Durante un proceso de cambio de fase de una
sustancia pura:
P y T no son propiedades independientes,
la presin P y la temperatura T son propiedades
dependientes,
Es decir P = f(T)

y por lo tanto no se pueden emplear para

identificar el estado de la sustancia segun el
postulado de estado para una sustancia pura,
simple compresible.

Temperatura de saturacin.
Presin de saturacin. ( Cont.)
Para una presin dada P, una sustancia pura
cambia de fase a una temperatura fija T
llamada temperatura de saturacin
Para una temperatura dada T, una sustancia
pura cambia de fase a una presin fija P
llamada presin de saturacin
Para el agua: Ps f EXP[g/(T+h)] con
f = 1,40974x107kPa

g = -3928.5C

h = 231,667C

Patm = Po EXP(-gz / RaT)

Po = 101.32 kPa
g = 9.81 m/s2
Ra = 287 J/kg-K
Tsat g/ln(Patm / f ) - h
f = 1,40974x107kPa
g = -3928.5C
h = 231,667C

Lquido comprimido o
subenfriado
Dependiendo del nivel de energa, una
sustancia pura puede existir en diferentes fases.
Si una sustancia est en fase lquida y en
estados alejado de la condicin de vaporizacin
se dice que es lquido comprimido o subenfriado.
Por ejem. Agua a Patm=86 kPa y 15C

Vapor recalentado o sobrecalentado

Si una sustancia est en fase gaseosa
(Vapor), y sus estados termodinmicos no
corresponden a la condicin para
condensacin, es un vapor recalentado
Ej.: Vapor de agua a
P = 101.3 kPa
T = 150 C
Est en fase gaseosa como vapor recalentado

Concepto de Calidad, x
En una mezcla saturada de lquido y vapor,
la fraccin msica de vapor se llama la
calidad x, definida como:
x =

m
m

vapor
total

0 x 1

m vapor
x =
m liq + m vapor

Lquido saturado:
Vapor saturado:

Vg , mg
Vf , mf

x=0
x=1

Diagrama T- v mostrando los puntos de lquido (f)

y vapor saturado (g)

Relaciones con el concepto de Calidad, x

V y m propiedades extensivas: aditivas

m = m f + mg
Definiciones

V = V f + Vg
V
v=
m

vf =

Vf
mf

vg =

Vg
mg

x=

mg
mtotal

(1 x ) =

mf
mtotal

Desarrollo
V Vg + V f Vg V f v g m g v f m f
v= =
=
+
=
+
m
m
m m
m
m

Vg , mg

mf
V mg
vg +
v f = xvg + (1 x )v f
v = =
m m
m

Vf , mf

Relaciones

v = xvg + (1 x )v f

x=

v vf
vg v f

v vf
v fg

Propiedades intensivas de una

mezcla saturada (de fases)
En la regin de mezclas saturadas, el valor promedio
de cualquier propiedad intensiva genrica y se puede
determinar conociendo la calidad x y los valores yf
del liquido saturado (f) y yg del vapor saturado (g)

y = xy g + (1 x) y f
y = y f + xy fg con y fg = y g y f
y : v, u, h, s

Saturated LiquidVapor Mixture

Quality, x : The ratio of the mass of vapor to the total mass of the mixture.
Quality is between 0 and 1
0: sat. liquid,
1: sat. vapor.
The properties of the saturated liquid are the same whether it exists alone or in
a mixture with saturated vapor.
Temperature and pressure
are dependent properties
for a mixture.
The relative
amounts of
liquid and vapor
phases in a
saturated
mixture are
specified by the
quality x.

A two-phase system can be

treated as a homogeneous
mixture for convenience.

v, u, or h.

Quality is related
to the horizontal
distances on P-v
and T-v diagrams.
The v value of a
saturated liquidvapor
mixture lies between
the vf and vg values at
the specified T or P.
25

PROPERTY TABLES

For most substances, the relationships among thermodynamic properties are too complex
to be expressed by simple equations.
Therefore, properties are frequently presented in the form of tables.
Some thermodynamic properties can be measured easily, but others cannot and are
calculated by using the relations between them and measurable properties.
The results of these measurements and calculations are presented in tables in a
convenient format.

EnthalpyA Combination Property

The combination
u + Pv is
frequently
encountered in
the analysis of
control volumes.

The product pressure

volume has energy units.

Tabla de
propiedades
del agua
Saturada

Saturated Liquid and Saturated Vapor States

Table A4: Saturation properties of water under temperature.
Table A5: Saturation properties of water under pressure.
A partial list of Table A4.

Enthalpy of vaporization, hfg (Latent

heat of vaporization): The amount of
energy needed to vaporize a unit mass of
saturated liquid at a given temperature or
pressure.

Tabla de
propiedades
del vapor de
agua
sobrecalentada

Ejemplo:
Para Agua:
Si T=90C determinar:
Presin de saturacin,
volumen especifico del
liquido saturado (x=0) y
del vapor saturado (x=1)
"Propiedades del Agua empleando EES"
T1 = 90 [C]
P_sat = P_SAT(Water,T=T1)
v_f = VOLUME(Water,T=T1,x=0)
v_g = VOLUME(Water,T=T1,x=1)
P_sat = 70.12 [kPa]
T1

= 90 [C]

v_f

= 0.001036 [m^3/kg]

v_g

= 2.362 [m^3/kg]

Ejemplo:
Para Agua:
Si P = 50 PSIa determinar:
Temperatura de saturacin,
volumen especifico del
liquido saturado (x=0) y
del vapor saturado (x=1)

"Propiedades del Agua empleando EES"

{sistema unidades Ingles (E)}
P1
T_sat
v_f
v_g
V
m
m
P1
T_sat
V
v_f
v_g

= 50 [PSI]
= T_SAT(Water,P=P1)
= VOLUME(Water,P=P1,x=0)
= VOLUME(Water,P=P1,x=1)
= 2 [ft^3]
= V/v_g
= 0.2346 [lb_m]
= 50 [PSI]
= 281 [F]
= 2 [ft^3]
= 0.01727 [ft^3/lb_m]
= 8.523 [ft^3/lb_m]

Ejemplo:
Para Agua:
Si P = 100 kPa determinar:
Temperatura de saturacin,
volumen especifico del
liquido saturado (x=0) y
del vapor saturado (x=1)

"Propiedades del Agua empleando EES"

{sistema unidades SI }
P1
= 100 [kPa]
T_sat = T_SAT(Water,P=P1)
v_f
= VOLUME(Water,P=P1,x=0)
v_g
= VOLUME(Water,P=P1,x=1)
rho_f = 1/v_f
rho_g = 1/v_g
P1
rho_f
rho_g
T_sat
v_f
v_g

= 100 [kPa]
= 958.7 [kg/m^3]
= 0.5897 [kg/m^3]
= 99.61 [C]
= 0.001043 [m^3/kg]
= 1.696 [m^3/kg]

Ejemplo: Para Agua:

Si T = 90 C mg = 2 kg mf = 8 kg
determinar:
Presion de saturacin,
volumen especifico del
liquido saturado (x=0) y
del vapor saturado (x=1)
Calidad x
volumen especifico de la mezcla

"Propiedades del Agua empleando EES"

{sistema unidades SI }
m_g
= 2[kg]
m_f
= 8[kg]
T1
= 90 [C]
P_sat
= P_SAT(Water,T=T1)
v_f
= VOLUME(Water,T=T1,x=0)
v_g
= VOLUME(Water,T=T1,x=1)
x
= m_g/m { def. calidad}
m
= m_g+m_f
{ Masa total}
v
= x*v_g+(1-x)*v_f { volumen esp. mezcla}

m
m_f
m_g
P_sat
T1
V
v_f
v_g
x

= 10 [kg]
= 8 [kg]
= 2 [kg]
= 70.12 [kPa]
= 90 [C]
= 0.4732 [m^3/kg]
= 0.001036 [m^3/kg]
= 2.362 [m^3/kg]
= 0.2

Ejemplo: Para R134a:

Si P = 160 kPa mg = 4 kg
mf = 6 kg determinar:
Temperatura de saturacin,
volumen especifico del
liquido saturado (x=0) y
del vapor saturado (x=1)
Calidad x
volumen especifico de la mezcla

"Propiedades del R134a empleando EES"

{sistema unidades SI }
m_g
= 4[kg]
m_f
= 6[kg]
P1
= 160 [kPa]
T_sat
= T_SAT(R134a,P=P1)
v_f
= VOLUME(R134a,P=P1,x=0)
v_g
= VOLUME(R134a,P=P1,x=1)
x
= m_g/m { def. calidad}
m
= m_g+m_f
{ Masa total}
v
= x*v_g+(1-x)*v_f { volumen esp. mezcla}
Vg
= m_g*v_g
Vf
= m_f*v_f
F_vol
= Vg/(Vf+Vg){fraccion volum del vapor}
F_vol=0.991
x=0.4
m=10 [kg]
m_f=6 [kg]
m_g=4 [kg]
P1=160 [kPa]
T_sat=-15.6 [C]
v=0.04984 [m^3/kg]
Vf=0.004462 [m^3]
Vg=0.4939 [m^3]
v_f=0.0007437 [m^3/kg]
v_g=0.1235 [m^3/kg]

In this region, In the region to the

right of the saturated vapor line
and at temperatures above the
critical point temperature, a
substance exists as superheated
vapor.
temperature and pressure are
independent properties.

Superheated Vapor
Compared to saturated vapor, superheated
vapor is characterized by

At a specified P,
superheated
vapor exists at a
higher h than the
saturated vapor.

A partial
listing of
Table A6.

35

The compressed liquid properties

depend on temperature much more
strongly than they do on pressure.

y v, u, or
h

Compressed Liquid
Compressed liquid is characterized
by

A more accurate relation for h

A compressed liquid
may be approximated as
a saturated liquid at the
given temperature.

At a given P and
T, a pure
substance will
exist as a
compressed
liquid if

36

Reference State and Reference Values

The values of u, h, and s cannot be measured directly, and they are calculated from measurable
properties using the relations between properties.
However, those relations give the changes in properties, not the values of properties at specified
states.
Therefore, we need to choose a convenient reference state and assign a value of zero for a
convenient property or properties at that state.
The referance state for water is 0.01C and for R-134a is -40C in tables.
Some properties may have negative values as a result of the reference state chosen.
Sometimes different tables list different values for some properties at the same state as a result of
using a different reference state.
However, In thermodynamics we are concerned with the changes in properties, and the reference
state chosen is of no consequence in calculations.

THE IDEAL-GAS EQUATION OF STATE

Equation of state: Any equation that relates the pressure, temperature, and
specific volume of a substance.
The simplest and best-known equation of state for substances in the gas phase is
the ideal-gas equation of state. This equation predicts the P-v-T behavior of a gas
quite accurately within some properly selected region.

Ideal gas equation of state

R: gas constant
M: molar mass (kg/kmol)
Ru: universal gas constant

Different substances have different gas

constants.

Mass = Molar mass Mole number

Ideal gas equation at two

states for a fixed mass
Various
expressions
of ideal gas
equation

Properties per
unit mole are
denoted with a
bar on the top.

Real gases behave as

an ideal gas at low
densities (i.e., low
pressure, high
temperature).

The ideal-gas relation

often is not applicable to
real gases; thus, care
should be exercised
when using it.

Ecuaciones de Estado
Para los gases ideales

: Constante Universal de los gases

PV = nT = nR T

= 8.31447 kJ/kmol

PV = mRT

R: Constante particular del gas

V
P = RT
m

Pv = RT

R
R=
=
PM PM

Para los gases reales

Pv = ZRT

Pv
Z=
RT

Z: Factor de compresibidad

COMPRESSIBILITY FACTORA MEASURE

OF DEVIATION FROM IDEAL-GAS BEHAVIOR
Compressibility factor Z A
factor that accounts for the
deviation of real gases from
ideal-gas behavior at a given
temperature and pressure.

The compressibility factor is

unity for ideal gases.

The farther away Z is from unity, the more the gas

deviates from ideal-gas behavior.
Gases behave as an ideal gas at low densities (i.e.,
low pressure, high temperature).
Question: What is the criteria for low pressure and
high temperature?
Answer: The pressure or temperature of a gas is high
or low relative to its critical temperature or pressure.

At very low pressures, all gases approach

ideal-gas behavior (regardless of their
temperature).

Reduced pressure

Reduced temperature
Pseudo-reduced
specific volume

Comparison of Z factors for various gases.

Z can also be determined from

a knowledge of PR and vR.

Gases deviate from the

ideal-gas behavior the
most in the neighborhood
of the critical point.

Z: Factor de compresibidad

El factor de compresibidad Z para el Nitrgeno

OTHER EQUATIONS OF
STATE
Several equations have been proposed to
represent the P-v-T behavior of substances
accurately over a larger region with no
limitations.

Van der Waals Equation of State

Critical isotherm
of a pure
substance has an
inflection point at
the critical state.

This model includes two effects not considered in the

ideal-gas model: the intermolecular attraction forces
and the volume occupied by the molecules
themselves. The accuracy of the van der Waals
equation of state is often inadequate.

Beattie-Bridgeman Equation of State

The constants are given in Table
34 for various substances. It is
known to be reasonably accurate
for densities up to about 0.8cr.

Benedict-Webb-Rubin Equation of State

The constants are given in Table 34. This equation can handle substances
at densities up to about 2.5 cr.

Virial Equation of State

The coefficients a(T), b(T), c(T), and so on, that are

functions of temperature alone are called virial coefficients.

Percentage of error involved in various equations of

state for nitrogen N2
(% error = [(|vtable - vequation|)/vtable] 100).

Complex equations of
state represent the P-v-T
behavior of gases more
accurately over a wider
range.

Is Water Vapor an Ideal Gas?

At pressures below 10 kPa, water

vapor can be treated as an ideal gas,
regardless of its temperature, with
negligible error (less than 0.1 percent).
At higher pressures, however, the ideal
gas assumption yields unacceptable
errors, particularly in the vicinity of
the critical point and the saturated
vapor line.
In air-conditioning applications, the
water vapor in the air can be treated as
an ideal gas. Why?
In steam power plant applications,
however, the pressures involved are
usually very high; therefore, ideal-gas
relations should not be used.

Percentage of error ([|vtable - videal|/vtable] 100) involved in assuming

steam to be an ideal gas, and the region where steam can be treated as an
ideal gas with less than 1 percent error.

N.B.
Latent heat: The amount of energy absorbed or released during a
phase-change process.
Latent heat of fusion: The amount of energy absorbed during
melting. It is equivalent to the amount of energy released during
freezing.
Latent heat of vaporization: The amount of energy absorbed during
vaporization and it is equivalent to the energy released during
condensation.
The magnitudes of the latent heats depend on the temperature (T) or
pressure (P) at which the phase change occurs.
At 1 atm pressure, the latent heat of fusion of water is hif = 333.7
kJ/kg and the latent heat of vaporization is hfg =2256.5 kJ/kg.
The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation.

Summary
Pure substance
Phases of a pure substance
Phase-change processes of pure substances
Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor
Saturation temperature and Saturation pressure

Property diagrams for phase change processes

The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface

Property tables
Enthalpy
Saturated liquid, saturated vapor, Saturated liquid vapor mixture,
Superheated vapor, compressed liquid
Reference state and reference values

The ideal gas equation of state

Is water vapor an ideal gas?

Compressibility factor
Other equations of state